Thioureido sulfonanilide compositions

ABSTRACT

WHEREIN R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R1 can be selected from lower alkyl, lower alkoxy and lower thioalkyl. The compounds are useful fungicides and biocides.   New compounds corresponding to the generic formula:

United States Patent [191 Mihailoyski Aug. 27, 1974 l THIOUREIDO SULFONANILIDE COMPOSITIONS [75] Inventor: Alexander Mihailovski, Berkeley,

[21] Appl. No.: 217,697

[52] US. Cl 260/470, 260/455 A, 260/552 R,

424/300, 424/321 [51] Int. Cl C07c 157/06 [58] Field of Search 260/552, 470, 455

[56] References Cited 6 OTHER PUBLICATIONS Martin, D. et al., Arch. Pharm. 296(10), pages 64l-650,(l963).

Primary ExaminerLorraine A. Weinberger Assistant ExaminerPaul .l. Killos Attorney, Agent, or Firm-Daniel C. Block ABSTRACT New compounds corresponding to the generic formula:

wherein R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R can be selected from lower alkyl, lower alkoxy and lower thioalkyl. The compounds are useful fungicides and biocides.

29 Claims, N0 Drawings 1 THIOUREIDO SULFONANTLIDE COMPOSITIONS DESCRlPTION OFTHE INVENTION This invention is directed to a-novel group of compounds which may be generally described as thioureido sulfonanilides which are highly active fungicides and biocides. The compounds of the present invention are represented by the generic formula:

' NH-SOz-R wherein R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R can be selected from-lower alkyl, lower alkoxy and lower thioalkyl.

The above compounds can be prepared by treating a Z-aminoalkylsulfonanilide o'r 2-aminoarylsulfonanilide withan appropriate carbonyl isothiocyanate in an inert solvent such as acetone orthe like. The products form .rapidly and can be isolated in good purity. v

In order to illustrate the merits of the present inven- ;tion the following example's'are provided.

EXAMPLE 1 Preparation of 2-[-3'-(Eth I benzenesulfonanilide .To. 5.0 g. (0.020 mole) V of 2- aminobenienesulfonanilide dissolved in 30 ml. of .ace-' tone' were added ,with stirring 2.6 g. (0.020 mole) filtered to give 7.4'g.'of 2-[3'-(ethoxycarbonyl)-thioureidol-methanesulfonanilideg -r'n.p.

Other compoundswere prepared in an analogous oxycarbonyl)-thioureido]- I manner starting with the appropriate starting. materials H t as outlined above. The following is a table of cornpoundsrep'resentative of those embodied by the pres-' ent invention. Compound numbers havebeen assigned to them and are used for identification throughout the balance of the specification.

TABLE I NHS O:'R

NH-C-NH-C-Ri Compound No. R R1.

1 OCHzCH3 CHa 2 CH; -0cir, a -CH; -ocmom 4 CH3 0H:CH3

- -oom TABLE I- Continued H V CompoundNo. R R1 8 H -OCH3 0; -oomom 11 CH'ZCH3 OCH3 l2 -CH2CH3 OCHzCH3 l3 CH2CH3 01120113 15 r -omcrn 16 0H; -.OH3

1a.. Q .opmomcm 19'. -omom'om }--0oH3 .204. 421201120113 1; OCH2CH3 2L -C'HgCHgCH; A 0CHzC HzCH3 22- -oH1cH2o1n-- --CH3 y w 2a .CH; -oominorn 24 1 --0oH-2oHom fem 115.

1 oomo'morra l w ot. 26 -oH,' 45011.601. 27 -crn a gsomon; 28 E 1 H r .-"o,; .c ni- -oH-i 20 ..-oin 1 g orn- A OCH2CH I "31 --s'cH2o 3" M -0o CH3.

as 7 -o om}cm .OCH2C as -ooHicH3 7 -cH,}-om a a j r as i -=0CHzCHaCHa cm on j: 31-. -cmoi -ocme m 3s orr, f OCHzCH3 I I FUNGICIDETESTING PROCEDURES A. Foliar Preventative Sprays TweenZO, a wetting agent; Test concentrations, ranging frorn 1000 ppm downward," ar'e sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulga'ris L. "Aftefr'the leaves are dried; they are inoculated with alwater suspension of spores of the bean rust fungus 4 (Urbmyces phlzseoli Arthur)and the plants are placed in an environment of 100 percent humidity for 24 hours. The plants are then removed from the humidity chamher and held, until disease pustules appear on the leaves. Effectiveness is recorded as the lowest concen- -tration, in ppm which will provide 50 percent reduction Iated plants; I g

2. Bean Powdery Mildew Test chemicals are prepared and applied in the same concentration are placed in a test tube. A pinto bean plant is placed in each tube and supported with a piece of cotton so that only the roots and lower stem are in contact with the test solution. Forty-eight hours later the bean leaves are inoculated with a water suspension of spores of the bean rust fungus and placed in an environment with 100 percent humidity for 24 hours. The plants are then removed from the humidity chamber and maintained in the greenhouse until the disease pustules appear on the IeavesEffectiveness is recorded as the lowest concentration, in ppm, whcih will provide 50 percent reduction in pustule formation as compared to untreated, inoculated ,plants.

2. Bean Powdery Mildewv I Test chemicals are prepared and applied in the same manner as forthe bean rust systemic test. After two days the leaves are dusted with spores of .the powdery in pustuleformation-as compared to untreated nocumanner as for the bean rust test. After the plants are dry, the leaves are dusted. with spores of the powdery mildew fungus (Erysiphe polygoni De Candolle) and the plants are retained in the greenhouse until the fungalgrowth appears on the leaf surface. Effectiveness is re'-' compared to untreated inoculated plantsQ mildew fungus and maintained in the greenhouse until mycelial growth appears on the leaf surfaces. Effectiveness is recorded as the lowest concentration, in ppm, which will provide a 50 percent reduction in mycelial growth on the leaf surface as compared to untreated, inoculated plants. j C. SystemicSoiI Drench 1; Bean Rust Pinto beansa re gro in ir siiirweiaaar 53511;;

I each containing 1 lb. of soil. Aliquots of the toxicant,

Test chemicals are prepared and applied in the same manner as the bean rust and powdery mildew tests except that 4-week old tomato (Lycopersicon esculentum) plants are utilized as the host plant. When the leaves are dry, they are inoculated with a water suspension of spores of the early blight fungus (Alternaris solani Ellis and Martin) and placed in an environment of IOOpercent humidity for 48 hours. The plants are then removed from the humidity chamber and held until disease lesions appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 50 percent reduction in number of lesions formed as compared to untreated inoculated plants.

B. Tube Systemic Te i 7 1. Bean Rust I g The chemicals are dissolved in an appropriate solvent and diluted with tap water to a series of descending concentrations beginning at 50 ppm. Sixty ml. of each comparison to untreated, inoculated plants.

- dissolved in an appropriate solvent, are diluted with 25 mL'of'water and drenched onto the soil surface. Two days late'rthebean leaves are inoculated with a water suspension of spores of the rust fungus, andthegplants are placed in .an' environment withv 100 percent humidity for 24 hours. The plantsare thenremoved from the humidity chamber and maintained the greenhouse untilthe pustules appear on' the leaves. Effectiveness is recorded as the minimum concentration, in ppm per Ib.

of soil, which will provide percent reduction in num ber of pustules as compared to untreatedinoculated v plant s.

2. Bean Powdery Mildew .The'bean plants and chemicals are prepared and plied'as in the rust systemic soil drench test. After ten days, the bean leaves are dusted with spores of the powdery mildew fungus and maintained in the greenhouse until the mycelial growth appears on the leaf surface.

Effectiveness is recorded as the minimum concentration, in ppm per lb. of soil, which will provide 50 percent reduction in mycelial growth on the leaf surface in "his" Com- Foliar Spray Tube Systemic Soil Drench pound No. Rust Mildew Tomato Blight Rust Mildew Rust Mildew I IO00 50 I0O0 I 6 2 1000 50 lO0O l 0.13 6 3 I000 5 0.25 55 6 4 l000 I000 l 55 5 1000 I00 IO00 1 55 6 I000 I00 5 55 7 I000 I000 8 I000 I00 I000 5 55 9 I000 50 IOO0 5 55 I0 I000 I000 ll I000 I00 5 0.13 55 13 I2 l000 500 I 55 I3 l00o I000 I4 I000 500 5 55 I5 I000 I000 I6 lO00 500 I0 17 I000 l000 TABLE ll -Continued (oml-oliur Spray 'luhc Systemic Soil Drench v pound No. Rust Mildew l'onmlo Blight Rust Mildew Rust Mildew Blocide Testing Procedures TABLE Ill-commuted Tubes of sterilized nutrient and malt extract broth Compound are prepared. Aliquots of the toxicant, dissolved in an 25 A, 5Q appropnate solvent, are in ected. through the stopper, H into the broth to rovide concentrations ran in from 34 50 50 50 50 P I g g 35 50 50 50 50 50 ppm downward. The test organisms consist of two 36 50 50 50 25 fung1,Asperg1IIus mger (A.n.) van T1eghem and Penlczl- 3; 3 50 :28 3? lium italicum (P.1.) Wehmer, and two bacterla, Escheri- 30 chia coli (E.c.) Migula and Staphylococcus aureus (S.a.) Rosenbach. Three drops of a spore suspension of each of the fungi are injected into the tubes of malt broth and three drops of the bacteria are injected into the nutrient broth. One week later the growth of each organism is observed and effectiveness of the chemical is recorded as the lowest concentration inppm which provides 50 percent inhibition of growth as compared to untreated inoculated tubes. The results of these tests are tabulated in Table 111.

TABLE III Compound No. A.n. P.i. E.c. S.a.

l (50) 5) 50 50 2 50 (1) 50 50 3 50 (l) 50 (50) 4 50 (25) 50 (50) 5 50 (5) 50 50 6 50 (I) 50 50 7 50 50 50 50 8 50 (50) 50 50 9 50 (50) 50 50 10 50 50 51) 50 ll 50 (25) 50 50 12 50 (25) 50 50 13 50 50 50 50 l4 50 25 50 50 15 50 50 50 50 16 50 50 50 50 17 50 50 50 50 18 50 50 50 50 19 50 50 50 50 20 550' 50 50 50 21 50 50 50 50 22 50 50 50 50 23 50 5 50 50 24 50 50 50 50 25 50 50 50 50 26 50 50 50 25 27 50 50 50 50 28 50 10 50 50 29 50 50 50 50 30 50 50 50 1 31 50 50 50 25 32 50 50 50 50 33 50 50 50 partial control The compounds of this invention are generally embodied into a form suitable for convenient application.

For example, the compounds can be embodied into pesticidal composition which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions'will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays;

propellants, such as dichlorodifluoromethane, etc. If

desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc. upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol sprays While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide. compound will comprise not more than about 15.0 percent by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0 percent by weight of the active pesticide compound.

What is claimed is:

1. Compounds corresponding to the generic formula:

wherein R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R can be selected from lower alkoxy and lower chloroalk- {A compound as set forth in claim 1 wherein R is and R1 is -OCHgCH3.

3. A compound as set forth in claim 1 wherein R is 'CH3 R1 is 'OCH3.

4. A compound as set forth in claim 1 wherein R is -Cl-l and R is -OCH Cll S. A compound as set forth in claim 1 wherein R is and R1 is OCH 6. A compound as set forth in claim 1 wherein R is and R is -OCH C H 7. A compound as set forth in claim 1 wherein R is and R iS OCH 8. A compound as set forth in claim 1 wherein R is and R1 is -OCH2CH3.

9. A compound as set forth in claim 1 wherein R is -CH CH and R. is -OCH 10. A compound as set forth in claim 1 wherein R is -CH CH and R, is -OCH CH 11. A compound as set forth in claim 1 wherein R is and lifts (fl-l3. 12. A compound as set forth in claim 1 wherein R is and R, is ociflcmcu I 13. A compound as set forth in claim 1 wherein R is ICHZCH2CH3 and R1 iS OCHa.

14. A compound as set forth in claim 1 wherein R is CHgCHgCHg and R1 is 'OCHgCHa.

15. A compound as set forth in claim 1 wherein R is -CH CH CH and R is -OCH CH CH 16. A compound as set forth in claim 1 wherein R is CH3 and R1 is 'OCH CH CHg.

17. A compound as set forth in claim 1 wherein R is and R is -OCH CH CH 18. A compound as set forth in claim 1 wherein R is and R1 iS 'OCH2CH2CH3. 19. A compound as set forth in claim 1 wherein R is -CH;, and R is -OCH CCl 20. A compound as'set forth in claim 1 wherein R is -CH;; and R1 is -O(CH2)3CH3.

21. A compound as set forth in claim 1 wherein R is -CH and R is CH: -OCHG 22. Acompound as set cliaiim 1 wherein is and R, is -o'cH.ccl;,.

23. A compound as set forth in claim 1 wherein R is and R1 is oo 24. Acompound set in claim 1 wherein R is and R is OiCH QCi-L. 25. A compound as set forth in claim 1 wherein R is Q and R1 is -ocmo and R, is oCH.cH'.f 

2. A compound as set forth in claim 1 wherein R is
 3. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -OCH3.
 4. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -OCH2CH3.
 5. A compound as set forth in claim 1 wherein R is
 6. A compound as set forth in claim 1 wherein R is
 7. A compound as set forth in claim 1 wherein R is
 8. A compound as set forth in claim 1 wherein R is
 9. A compound as set forth in claim 1 wherein R is -CH2CH3 and R1 is -OCH3.
 10. A compound as set forth in claim 1 wherein R is -CH2CH3 and R1 is -OCH2CH3.
 11. A compound as set forth in claim 1 wherein R is
 12. A compound as set forth in claim 1 wherein R is
 13. A compound as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -OCH3.
 14. A compound as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -OCH2CH3.
 15. A compound as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -OCH2CH2CH3.
 16. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -OCH2CH2CH3.
 17. A compound as set forth in claim 1 wherein R is
 18. A compound as set forth in claim 1 wherein R is
 19. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -OCH2CCl3.
 20. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -O(CH2)3CH3.
 21. A compound as set forth in claim 1 wherein R is -CH3 and R1 is
 22. A compound as set forth in claim 1 wherein R is
 23. A compound as set forth in claim 1 wherein R is
 24. A compound as set forth in claim 1 wherein R is
 25. A compound as set forth in claim 1 wherein R is
 26. A compound as set forth in claim 1 wherein R is (CH2)3CH3 and R1 is -OCH2CH3.
 27. A compound as set forth in claim 1 wherein R is (CH2)3CH3 and R1 is -OCH2CH2CH3.
 28. A compound as set forth in claim 1 wherein R is -CH2Cl and R1 is -OCH2CH3.
 29. A compound as set forth in claim 1 wherein R is 